Mordanted imbibition dye-printing blank



Patented Apr. 10, 1951 MORDAN TED IMBIBITION DYE-PRINTING BLANK -Walter J. Wcyerts, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application October 15, 1948, Serial N 0. 54,7 96

13 Claims. (Cl. 101-149.1)

This invention relates to a photographic imbibition dye printing process and more particularly to improved imbibition dye printing blanks.

The imbibition dye printing process is well known. According to the common procedures, a tanned colloid relief image is formed by exposure of a suitable sensitive layer on a support and differentially hardening the colloid layer, thereafter removing the colloid from the support in the regions not exposed by light. The resultant colloid relief image is then dyed and the dye image transferred to a blank by imbibition. In this manner subtractively colored dye images may be obtained which faithfully reproduce a colored subject.

In the copending Sprague and Brooker U. S. applications Ser. Nos. 719,623 and 719,624 now Patent No. 2,484,430, both filed December 31, 1946, are described polymerized quaternized vinyl-substituted azine and azole dye-mordants which are especially suitable for mordanting imbibition dye printing blanks previous to printing. I have found that under certain conditions when using blanks containing such mordants, there appears to be a tendency for the mordant or difiusible constituents thereof, to diffuse out of the blank into the matrix in contact therewith as shown in Fig. 1 of the accompanying drawings. The result is that as repeated dye transfers are made from a given matrix more mordant diffuses into the matrix, combines with some of the dye and is held there. The matrix then takes up more dye than it should when it is re-dyed. When a transfer is made from the redyed matrix more dye is imbibed onto the blank thanoriginally and the color balance of a print is seriously altered. After a number of transfers, the matrix may become clogged resulting in a drop in the higher densities with repeated transfers. A further result is that since the diffusible constituents of the blank appear to diffuse back not only into the matrix but also are adsorbed by the bared areas of the matrix sup port representing the highlights of the picture, the final print contains undesirable dye density in the highlight region. I have discovered that when acidic polymeric materials are incorporated into a stratum at the surface of such mordanted blanks the undesirable effects of the mordanted blanks can be avoided. I

Therefore, one object of my invention is to provide an improved mordanted imbibition blank. Another object is to provide a process of making dye imbibition prints of improved quality by means of an improved imbibition blank.

2 Other objects will become apparent from the following description of my invention.

In the accompanying drawings, in Fig. 1 is illustrated the manner in which diifusible mordant molecules or particles migrate from an imbibition blank to a matrix film with the adverse effects mentioned. In Fig. 2 is shown a similar view of the improved colloid blank of the invention. Fig. 3 is a view similar to Fig. 1 showing the manner in which the blank of Fig. 2 improves the quality of dye transfers and prevents clogging of the matrix and staining of the support. 7

The objects of my invention are in part accomplished by applying a solution of a polymeric organic material containing a free acid group to the surface of a colloid imbibition dye printing blank containing a polymerized and quaternized vinyl-substituted azine dye-mordant. jects are accomplished by transferring a soluble acid dyestuff image from a matrix to this blank where it becomes fixed therein by reaction with the mordant.

The particular type of imbibition blank to which my process is applied is, as previously mentioned, one containing dispersed in a hydrophilic colloid layer such as gelatin or other material such as a Water-permeable resin like polyvinyl alcohol, a polymerized quaternized vinylsubstituted azine dye-mordant, such as disclosed in the mentioned copending applications. The mordants are quaternized derivatives of polymerized vinyl-substituted azines such as vinyl quinoline, vinyl acridine, vinyl pyridine, particularly 2- and 4-vinyl pyridine and other heterocyclic compounds containing nitrogen atoms. ,The quaternization may have been effected before or after polymerization by reacting with an alkyl sulfate or alkyl-p-toluene sulfonate. The 2-vinylpyridine polymer alko-p-toluenesulfonate 'mordants are especially useful. I

The polymeric organic materials containing a free acid group, which are used for treating the imbibition blank according to the invention, comprise an appreciable group of polymeric materials, which are almost non-diffusing in the colloid layer such as gelatin, some of Which may be soluble in water and alkaline solutions such as polymerized acrylic acids including polyacrylic acid, polymethacrylic acid and homologues thereof, maleic anhydride-vinyl acetate copolymers, carboxymethyl celluloses; and alkali soluble polymers such as acrylic ester-acrylic acid copolymers, e. g., methacrylic acid-methyl methacrylate resins, as well as polyvinyl phthal- Other obates and cellulose phthalates. Similarly, polymers containing sulfonic acid groups may be used such as polystyrene sulfonic and carboxylic acids and copolymers thereof with other vinyl compounds. Polymeric materials selected from the above groups comprise a preferred embodiment of my invention since the optimum results are obtained by their use in imbibition blanks.

My invention will now be described with reference to the accompanying drawing.

Fig. 1 shows an enlarged cross-sectional view of the elements concerned, the manner in which diffusible, perhaps low molecular weight mordant particles, wander out of the colloid layer ll of gelatin carried on paper support 10 into the dyed relief image 12 and film support 13, when dye is being transferred to the colloid blank to be mordanted onto mordant particles I5. As mentioned, this diffusion may clog the relief image, and adsorbed mordant on the support E3 or in a subbing layer thereon results in staining the highlight region of the print.

However, if I substitute for the blank of Fig. l, the blank of my invention shown in Fig. 2, the difiiculties attributed to mordant diffusion are avoided. The blank is prepared in a very simple manner. I first mordant a colloid layer such as a gelatin layer carried by a support with a mordant as described in the Sprague et al. inventions. This may be accomplished by adding the mordant in suitable quantity to a gelatin solution with hardener and coating the solution on a support to yield the blank of Fig. 2 wherein the support Id of paper or film is shown as carrying the gelatin layer II in which are dispersed diffusible and less diffusible mordant particles 14 and I5. Thereafter, I may merely bathe the blank for a short time in an aqueous solution of about 0.1% polyacrylic acid resin adjusted to pH 'of about 5.5 with sodium hydroxide solution. If

desired, the resin may be coated over the colloid surface from such a solution which may in addition contain a vehicle such as gelatin. This treatment of the blank appears to deposit the resin in high concentration in an outer stratum of the blank substantially as shown in Fig. 2 according to which support ii] carries the colloid layer 1 l containing diifusihle and non-diffusible particles Hi and i and a stratum of acid resin particles I6 and some particles I l which may result from reaction between mordant and resin. When the blank of Fig. 2 is used for receiving transfers of dye images from dyed relief images, photographic quality is improved in the manner shown in Fig. 3 of the drawings. The diffusible mordant particles l4 wandering toward the matrix film meet resin particles [6 and reacting therewith are prevented from wandering into the matrix film, the dye molecules I2 transferring undisturbed to be fixed on mordant particles I55 by reaction therewith.

When treating the mordanted blanks with the high molecular weight acids, I find that it may be desirable to regulate the pH of the system. However, most of the resins are effective over a moderate range of pH particularly from about 4.5 to 6.5. Polymeric materials which are not watersoluble are ordinarily used in the form of their alkali metal salts and in the case of a salt such as sodium polyvinyl phthalate, the pH of the treating or coating solution should be above 5.0 to prevent precipitation. Also, the pI-I should not be too low since the transfer of dyes into colloid blanks such as gelatin may be adversely affected.

4 Similarly, highconcentrations of the polymeric acid or salt thereof will influence dye transfer.

Other variations of my invention will become apparent to those skilled in the art and my invention is to be taken as limited only by the scope of the appended claims.

What I claim is:

1. A premordanted dye imbibition blank comprising a support having thereon a layer of hydrophilic colloid containing a polymerized quaternized vinyl-substituted azine dye-mordant and in only the outer stratum of said layer a polymeric organic material containing free acid groups and soluble in alkaline solutions.

2. A premordanted dye imbibition blank comprising a support having thereon a layer of hydrophilic colloid containing a quaternized polyvinyl pyridine dye-mordant and in only the outer stratum of said layer a polymeric organic material containing free acid groups and soluble in alkaline solutions.

3. A premordanted dye imbibition blank comprising a support having thereon a layer of hydrophilic colloid containing a quaternized polyvinyl pyridine dye-mordant and in only the outer stratum of said layer a polymeric material selected from the class consisting of water-soluble polymerized acrylic acids, maleic anhydride-vinyl ester co-polymers and carboxy methyl celluloses and alkali soluble acrylic ester-acrylic acid copolymers, polyvinyl phthalates and cellulose phthalates.

l. A premordanted dye imbibition blank comprising a suport having thereon a layer of hydrophilic colloid containing a quaternary ammonium salt of polyvinyl pyridine as a dye mordant and in only the outer stratum of said layer as an agent preventing diffusion of said mordant when said layer is wetted, a polymerized organic material selected from those set forth in claim 3.

5. A premordanted dye imbibition blank comprising a support having thereon a layer of hydrophilic colloid containing a 2-vinylpyridine polymer alko-p-toluene sulfonate dye-mordant and in only the outer stratum of said layer as an agent preventing diffusion of said mordant, a polymeric organic material containing free carboxyl groups.

6. The process for the manufacture of a dye imbibition blank which comprises applying a polymeric organic material containing free acid groups and soluble in alkaline solutions to the surface of a colloid blank containing a polymerized quaternized vinyl-substituted azine dyemordant.

7. The process for the manufacture of a dye imbibition blank which comprises applying to the surface of a gelatin blank containing a polymerized quaternized vinyl-substituted azine dyemordant, a polymeric organic material selected from those set forth in claim 3.

8. The process for the manufacture of a dye imbibition blank which compries applying to the surface of a gelatin blank containing a quater nary ammonium salt of polyvinyl pyridine as a dye mordant, a polymeric organic material selected from those set forth in claim 3 to prevent diffusion of said mordant in said blank.

9. The process for the manufacture of a dye imbibition blank which comprises, applying to the surface of a gelatin blank containing a 2- vinyl pyridine polymer alko-p-toluene sulfonate dye-mordant, a polymeric organic material containing free carboXyl groups to prevent diffusion of said mordant in said blank.

10. In a relief imbibition printing process wherein a soluble acid dyestuff is transferred from a colloid relief image to a colloid blank containing a polymerized quaternized vinyl-substituted azine dye-mordant, the process of fixing said dye-stuff in said blank which comprises treating the surface of said blank with a polymeric organic material containing free acid. groups and soluble alkaline solutions and then reacting said dyestuff with said mordant.

11. In a relief imbibition printing process wherein a soluble acid dyestuff is transferred from a colloid relief image to a gelatin blank containing a polymerized quaternized vinyl substituted azine dye-mordant, the process of fixing said dyestufi in said blank which comprises treating the surface of said blank with a polymeric organic material selected from those set forth in claim 3 and then reacting said dyestufi with said mordant.

12. In a relief imbibition printing process wherein a soluble acid dyestufi is transferred from a colloid relief image to a gelatin blank containing a quaternary ammonium salt of polyvinyl pyridine as a dye mordant, the process of fixing said dyestuff in said blank which comprises treating the surface of said blank with a polymeric organic material selected from those set forth in claim 3 and then reacting said dye-'- stuff with said mordant.

13. In a relief imbibition printing process wherein a solube acid dyestufi is transferred from a colloid relief image to a gelatin blank containing a 2-vinylpyridine polymer alko-p-toluene sulfonate dye mordant, the process of fixing said dyestuff in said blank which comprises treating the surface of said blank with a polymeric organic material containing free carboxyl groups and then reacting said dyestulf with said mordant.

WALTER J. WEYERTS.

No references cited. 

3. A PREMORDANTED DYE IMBIBITION BLANK COMPRISING A SUPPORT HAVING THEREON A LAYER OF HYDROPHILIC COLLOID CONTAINING A QUATERNIZED POLYVINYL PYRIDINE DYE-MORDANT AND IN ONLY THE OUTER STRATUM OF SAID LAYER A POLYMERIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF WATER-SOLUBLE POLYMERIZED ACRYLIC ACIDS, MALEIC ANHYDRIDE-VINYL ESTER CO-POLYMERS AND CARBOXY METHYL CELLULOSES AND ALKALI SOLUBLE ACRYLIC ESTER-ACRYLIC ACID COPOLYMERS, POLYVINYL PHTHALATES AND CELLULOSE PHTHALATES. 